(thiono) phosphoric (phosphonic)-acid esters

ABSTRACT

Esters of (thiono) phosphoric or phosphonic acid esters and ester amides as the acid moiety and (3-methyl-5-hydroxypyrazolyl-1)-(thiono) phosphoric or phosphonic acid esters as the alcohol moiety, which possess arthropodicidal, especially acaricidal and insecticidal, properties, and which may be produced by conventional methods.

United States Patent Hoffmann et al.

[ Oct. 24, 1972 (THIONO) PHOSPIHORIC (PHOSPHONIC)-ACID ESTERS [72]Inventors: Hellmut Hoffmann, Wuppertal-Elberfeld; Ingeborg Hammann,Cologne; Bernhard Homeyer, Opladen, all of Germany [73] Assignee:Farbenfalbriken Bayer Aktiengesellschaft, Leverkusen, Germany [22]Filed: March 31, 1970 [21 AppL No.: 24,397

130] Foreign Application Priority Data April 15, 1969 Germany ..P 19 17741.4

[52] US. Cl. ..260/310 R, 260/923, 424/200 [51 Int. Cl. ..C07d 49/18,C07f 9/40 [58] Field of Search ..260/310 R [56] References Cited UNITEDSTATES PATENTS 2,754,244 7/1956 Gysin et al. ..260/310 R 3,216,89411/1965 Lorenz et a1. ..260/310 R 3,232,830 2/1966 Schrader et a]...260/310 R FOREIGN PATENTS OR APPLICATIONS 300,741 10/1954 Switzerland..260/3 l0 R 300,758 10/1954 Switzerland ..260/310 R OTHER PUBLICATIONSAbramov et a]. J. Gen. Chem. (USSR) Vol. 38, Page 2715 (1968).

Arbuzov et al. Chem. Abst. Vol. 60, Columns 4127- 4128 (1964).

Chemical and Engineering News Vol. 30, No. 43, Pages 4513- 4526 (1952,Oct. 27, 1952).

Zinov ev J. Gen. Chem. (USSR) Vol. 39, Pages 574- 575 (1969, Mar.1969,).

Primary Examiner-Natalie Trousof Attorney-Burgess, Dinklage & Sprung lABSTRACT Esters of (thiono) phosphoric or phosphonic acid esters andester amides as the acid moiety and [3-methyl-5-hydroxy-pyrazolyl-1]-(thiono) phosphoric or phosphonic acidesters as the alcohol moiety, which possess arthropodicidal, especiallyacaricidal and insecticidal, properties, and which may be produced byconventional methods.

12 Claims, No Drawings (THIONO) PHOSPHORIC (PHOSPHONIQ-ACID 'ESTERS Thepresent invention relates to and has for its objects the provision ofparticular new esters of (thiono) phosphoric or phosphonic acid estersand ester amides as the acid moiety and[3-methy1-5-hydroxy-pyrazolylll-(thiono) phosphoric or phosphonic acidesters as the alcohol moiety, which possess arthropodicidal, especiallyinsecticidal and acaricidal, properties, active compositions in the formof mixtures of such compounds with solid and liquid dispersible carriervehicles, and methods for producing such compounds and for using suchcompounds in a new way especially for combatting pests, e.g.,arthropods, especially insects and acarids, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

From US. Pat. No. 2,754,244 it is known that0,0-dialkyl--[3-methyl-pyrazolyl-(5)-phosphoric andthiono-phosphoric-acid acid esters possess insecticidal and acaricidalactivity.

It has now been found, in accordance with the present invention, thatthe particular new (thiono) phosphoric (phosphonic)-acid esters andester amides of the general formula no X \IILN--N R U RY 0H:

\P o 12 2i, (I)

in which R and R' are straight-chain or branched lower alkyl X and X areoxygen or sulphur,

R" is straight-chain or branched lower alkyl, lower alkoxy, mono-loweralkylamino or di-lower alkylamino or aryl,

R is straight-chain or branched lower alkyl or lower alkoxy,

exhibit strong arthropodicidal, especially insecticidal and acaricidal,properties.

It has been furthermore found, in accordance with the present invention,that the particular new compounds of formula (I) above may be producedby a process which comprises reacting an alkali metal salt ofsubstituted pyrazole of the general formula Ro\) |r /PNN R I IL in whichR,R and X have the abovementioned significance and M is an alkali metal,preferably sodium, with a (thiono) phosphoric (phosphonic)-acid esterhalide or -amide halide of the general formula it? til 2 in which R', R"and X have the abovementioned significance and Hal is halogen,preferably chlorine or bromine.

Surprisingly, the particular new (thiono) phosphoric (phosphonic)-acidesters and ester amides of formula (I) above according to the inventionpossess a significantly higher insecticidal and acaricidal action,especially a considerably better activity against sucking and bitinginsects than the 0,0-dialkyl-O-[3-methylpyrazolyl-(5)]-phosphoricandthionophosphoric-acid esters of analogous constitution known from thepatent specification mentioned above. The compounds of the presentinvention therefore represent a valuable contribution to the art.

Where 0,0-diethyl-thionophosphoric-acid ester chloride and the sodiumsalt of 0,0-diethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphoric-acid ester are used as startingsubstances for the process, the course of the reaction can beillustrated by the following formula scheme:

The pyrazole derivatives and the acid halides to be used for themanufacturing process are clearly defined by the general formulas (II)and (III), respectively, given above.

Advantageously, in accordance with the present invention, in the variousformulas herein:

R AND R' represent straight and branched chain lower alkyl of one tofour carbon atoms such as methyl, ethyl, nand iso-propyl, 11-, iso-,sec.- and tert.-butyl, and the like, especially C alkyl;

R' represents straight and branched chain lower alkyl or lower alkoxy ofone to four carbon atoms such as methyl to tert.-butyl and methoxy totert.-butoxy inclusive as defined above, and the like, and especially Calkyl or alkoxy;

R" represents aryl or straight or branched alkyl, alkoxy, monoalkylaminoor dialkylamino with one to four carbon atoms in each alkyl group, andpreferably phenyl or straight or branched alkyl, alkoxy, monoalkylarninoor dialkylamino with one to three carbon atoms in each alkyl group;

X and X represent oxygen or sulphur, and

Y represents oxygen, NH- or NR The alkali metal salts, preferably sodiumsalts, of the pyrazole derivatives of formula (II) which are used asstarting materials are not known but can be made by reacting alkalimetal alcoholates with the appropriate phosphorylatedhydrazonocarboxylic acid ester derivatives with ring closure occurringin accordance with the following formula scheme:

As examples of pyrazole derivatives of formula (II) above which can beused according to the present invention, there may be mentioned, forinstance: the alkali metal salts such as lithium or potassium butpreferably sodium salts, of l-(0,0-dimethyl-phosphoryl)-, l-(0,0-diethyl-phosphoryl)-, l-(0,0-dipropylphosphoryl)-,l-(0,0-di-iso-propyl-phosphoryl)-, l-(O- ethyl-O-butyl-phosphoryll-(0,0-di-sec.-butylphosphoryl)-, l-(O-methyl-methane-phosphonyl)-, l-(O-ethyl-ethane-phosphonyl l-( O-propyl-methanephosphonyl)-,propyl-methane-phosphonyl)-, l-(O-isopropyl-ethane-phosphonyl l-(O-butyl-ethanephosphonyl)-, l-( -tert. butyl-tert. butane-phosphonyl)-as well as l-(O-methyl-0-ethyl-phosphoryl)- and l-(O-ethyl-0-propyl-phosphoryl)-3-methyl-5-hydroxypyrazoles, and thecorresponding thionophosphoryl and thionophosphonyl derivatives.

Examples of acid halides of formula (III) which can be used according tothe present invention include the following: 0,0-dimethyl-,0,0-diethyl-, 0,0-dipropyl-, 0,0-di-iso-propyl-, 0,0-dibutyl-,0,0-di-sec.-butyl, O- methyl-O-ethyl-, O-ethyl-O-propyl-phosphoric-acidester chlorides, O-methyl-methane, O-ethyl-ethane-, 0- propyl-propane-,0-iso-propyl-ethane-, O-methyl-phenyl-, ()-cthyl-phenyl-,0-propyl-phenyl-, O-butyl-phenyl-, 0-sec.-butyl-phenyl-phosphonic-acidester chloride and bromide and their thiono analogues, di-( N,N-dimcthyl)-, di-(N,N-diethyl)-, di-(N,N-di-propyl)- and di-(N,N-dibutyl)-phosphoric-acid diamide chloride and bromide and thecorresponding thiono compounds, as well asO-ethyl-N-isopropylphosphoric-acid ester amide chloride and thethiono-analogue.

The production reaction is preferably carried out in the presence of asolvent (which term includes a mere diluent). As such, practically allinert organic solvents are suitable. These preferably include(optionally chlorinated) hydrocarbons, such as benzine, benzene,toluene, xylene, chlorobenzene as well as dichloromethane,dichloroethane, chloroform, carbon tetrachloride and the like; ethers,for example diethyl and dibutyl ether, dioxan; as well as low-boilingaliphatic ketones, for example acetone, methylethyl ketone,methylisopropyl ketone, methylisobutyl ketone and the like.

The reaction temperatures can be varied within a fairly wide range. ingeneral, the reaction is carried out at substantially between about 0 to100 C, and preferably between about 40 to 70 C. The reaction isgenerally carried out at atmospheric pressure.

In carrying out the process, the starting substances are generallyemployed in equimolar ratios. The reaction may be made to take place inthe usual manner by bringing the reactants together in one of theabovementioned solvents. After stirring the mixture for several hours atelevated temperature, it is poured into water and extracted by shakingwith benzene, and the solvent is subsequently distilled off afterdrying.

The (thiono) phosphoric (phosphonic)-acid esters and ester amidesaccording to the invention are mostly obtained in the form of colorlessto slightly yellowcolored, viscous, water-insoluble oils which cannot bedistilled without decomposition; they can however be freed of the lastvolatile constituents by so-called slight distillation, i.e., byprolonged heating under reduced pressure to moderately elevatedtemperatures, and can be purified in this manner. They are readilycharacterizable by their refractive indices.

As already mentioned above, the compounds according to the presentinvention are distinguished by outstanding insecticidal and acaricidalproperties. They possess at the same time excellent activity bothagainst insects which attack plants through the leaf and against harmfulsoil insects, as well as household pests and pests of stored products.The new substances furthermore in part show fungicidal activity againstgenuine mildew fungi and furthermore cause inhibition of growth orstoppage of growth when used in larger amounts. They can also be used asrodenticides. The

pesticidal action starts rapidly and continues for a long time. For thisreason the compounds according to the invention may be used in plantprotection and in the protection of stored products, as well as inhygiene for combating sucking and biting insects, Diptera and mites(Acarina). In this context, the excellent activity of the productsagainst phosphoric acid ester-resistant strains of spider mites shouldbe particularly mentioned.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi.),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus korschelti), the mealyapply aphid (Sappaphis mali), the mealy plum aphid (Hyalopterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleander scale (Aspidiotushederae) and the soft scale (Lecanium hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips Thysanoptera), such asHercinothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the cotton bug (Dysdercus intermedius), the bed bug (Cimexlectularius), the assassin bug (Rhodnius prolixus) and Chagas bug(Triatoma infestans) and, further, cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all thereshould be mentioned butterfly caterpillars lepidoptera) such as thediamond-back moth (Plutella maculipennis), the gipsy moth (Lymantriadispar), the brown tail moth (Euproctis chrysorrhoea) and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestrabrassicae) and the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygmafrugiperda) and cotton worm (Prodenia litura), the ermine moth(Hyponomeuta padella), the Mediterranean flour moth (Ephestia Kuhniella)and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein arebeetles (Coleoptera), for example the granary weevil (Sitophilusgranarius Calandra granaria), the Colorado beetle (Leptinotarsadecemlineata), the dock beetle-(Gastrophysa viridula), the mustardbeetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil (BruchidiusAcanthoscelides obtectus), the leather beetle (Dermestes frischi), thekhapra beetle (Trogoderma granarium), the flour beetle (Triboliumcastaneum), the northern corn billbug (Calandra or Sitophilus zeamais),the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebriomolitor) and the sawtoothed grain beetle (Oryzaephilus surinamensis),but also species living in the soil, for example wireworrns (Agriotesspec.) and larvae of the cockchafer (Melolontha melolomha); cockroaches,such as the German cockroach (Blattella germanica), American cockroach(Periplaneta americana), Madeira cockroach (Laucophaea or Rhyparobiamadeirae), Oriental cockroach (Blatta orientalis), the giant cockroach(Blaberus giganteus) and the black giant cockroach (Blaberus fuscus aswell as Henschoutedenia flexivitta; further, Orthoptera, for example thehouse cricket (Acheta domesticus); termites such as the easternsubterranean termite (Reticulitermes flavipes) and Hymenoptera such asants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Fannia caniculan's) the black blow fly (Phormia aegina) andbluebottle fly (Calliphora erythrocephala) as well as the stable fly(Stomoxys caleitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipiens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (Tetranychus telarius Tetranychus althaeae or Tetranychusurticae) and the European red mite (Paratetranychus pilosus Panonychusulmi), blister mites, for example the currant blister mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, suchas the relapsing fever tick (Ornithoa'orus moubata); and the like.

Significantly, when used against household pests and pests of storedproducts, particularly flies and mosquitoes, the instant activecompounds are also distinguished by an outstanding residual effect onwood and clay as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e., plant compatible or herbicidally inert)pesticide diluents or extenders, i.e., diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.,conventional pesticide dispersible carn'er vehicles such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticide dispersible liquid diluent carriers and/ordispersible solid carriers optionally with the use of carrier vehicleassistants, e.g., conventional pesticide surface-active agents,including emulsifying agents and/or dispersing agents, whereby, forexample, in the case where water is used as diluent, organic solventsmay be added as auxiliary solvents. The following may be chieflyconsidered for use as conventional carrier vehicles for this purpose:inert dispersible liquid diluent carriers, including inert organicsolvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene,etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.,chlorobenzenes, etc.), paraffins (e.g., petroleum fractions),chlorinated aliphatic hydrocarbons (e.g., methylene chloride, etc.),alcohols (e.g., methanol, ethanol, propanol, butanol, etc.), amines(e.g., ethanolamine, etc.), ethers, ether-alcohols, (e.g., glycolmonomethyl ether, etc.), amides (e.g., dimethyl formamide, etc.),sulfoxides (e.g., dimethyl sulfoxide, etc.), ketones (e.g., acetone,etc.) and/or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g., kaolins, alimina,silica, chalk, i.e., calcium carbonate, talc, kieselguhr, etc.) andground synthetic minerals (e.g., highly dispersed silicic acid,silicates, e.g., alkali silicates, etc. whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g., surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and/or anionic emulsifying agents (e.g., polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides and insecticides, or rodenticides, fungicides, herbicides, bactericides, etc.,if desired, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1-95 percent byweight, and preferably 0.5- percent by weight, of the mixture, whereascarrier composition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.00001-20 percent,preferably 0.0l5 percent by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (l) a dispersibleinert finely divided cam'er solid, and/or (2) a dispersible carrierliquid such as an inert organic solvent and/or water preferablyincluding a surface-active effective amount of a carrier vehicleassistant, e.g., a surface-active agent, such as an emulsifying agentand/or a dispersing agent, and an amount of the active compound which iseffective for the purpose in question and which is generally betweenabout 0.0000l-95 percent, and preferably 0.0l95 percent, by weight ofthe mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e., by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e. g., average particle diameter of from 50-100 microns,or even less, i.e., mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95 percent by weight ofactive compound or even the 100 percent active substance alone, e.g.,about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g., arthropods, i.e., insectsand acarids, and more particularly methods of combating at least one ofinsects and acarids which comprises applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, and (c) thecorresponding habitat thereof, i.e. the locus to be protected, acorrespondingly combative or toxic amount, i.e., an arthropodicidally,especially insecticidally or acaricidally, effective amount of theparticular active compound of the invention alone or together with acarrier vehicle as noted above. The instant formulations or compositionsare applied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples EXAMPLE 1 Phaedon larvae testSolvent Emulsifier: 3 parts by weight acetone TABLE 1 Phaedon larvaetest Active compound Degree of conceutradestruction tion in in percentActive compound (constitution) percent after 3 days (A). t i 0. 1 0

(CHaO); POI

HN N J 0 H3 (known) (2) o O. 1 100 H 0.01 100 (C H3O); PN-N (CHaO)2}|OCH3 (3) a 0. 1 100 ll 0. 01 100 (CH 0)2 PN-N ((321150) fi-O- CH:

(4) S O. 1 100 ll 0. 01 100 (CH O)2PNN (C2H5 O)2 :fi0K/ CH (5). S 0. l100 11 0. 01 100 (C2H5O)2 (C 3 )2fi-0 CH;

(6).." O 0.l 100 0. 01 (0 150); PNN

(CH O)Z}I O CH3 (1). S 0. 1 H 0.01 100 (C H5O)2PN--N 0.001 100(CHsChfi-O CH3 (7) S 0. 1 100 II 0.01 100 (CgH5 )zP-NN (Cgl 50)zP-O-0113 TABLE 1 Continued Phaedon larvae test Active compound Degree ofconeentradestruction tion in in percent Active compound (constitution)percent after 3 days (CH30)2 PN-N CgHs fi-O CH3 CzHs 0 S O. 1 100 (w) uo. 01 100 (C2115 0): PN-N CzHr-P-O S 0. 1 100 (m ll 0. 01 100 (CzHsO):PNN

CzH50fiO CH3 CzHs OPI?'N (CHgO); fi-OQLC H3 cgHs O- P-N N (CgHsO) i-OH-CH:

S O. 1 100 (mm 11 0.01 95 CzH50- P-N N (CzHsO)g:Jl] O CH;

C2 5 O-PNN CzH5-I|O -CH; CzH O s (CzH50)2PNN (C :)zNPO CH3 shN 0 01H; 0-P-N-'N (CH;);NPO CH;

EXAMPLE 2 Plulella res:

Solvent Emulsifier:

3 parts by weight of acetone 1 art by weight of alkylaryl polyglycolether To produce a suitable preparation of the particular activecompound, 1 part by weight of the active compound is mixed with thestated amount of solvent containing the stated amount of emulsifier andthe concentrate is diluted with water to the desired finalconcentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dew moist and are then infested withcaterpillars of the diamondback moth (Plutella maculipennis).

can be seen from Table 2.

TABLE 2 Plutella test Active com- Degree 0! pound condestructioncentration in percent Actlve compound (constitution) in percent after 3days (A) O. l 0

crI30)z1 o-' (known) (B) S 0. 1 100 .i 0. 01 0 (CgH50)zP-() \N/ CH3(known) (C1130): P N N (CgH50)gPO CII3 (5). S 0. l 100 ii 0. 01 100 (CH5O) P-N i 0.001 100 6 O O. l 100 5; 0.01 100 (CH30hl-O -CH3 s 0. 1 100(I) 0. 01 100 (CzH OM P-.\'-N 04 001 100 (CzHsO) lf-O CH (C2H50)z PN'-N(CzH50)gI?O CH3 .Y (J U. 1 100 n 0.01

(CzHsOh P-i\ -'N (CZHSO)IP OAK/H-"C Hz TABLE z 'k'munued Plutella testActive com- Degree of pound condestruction centration in percent Activecompound (constitution) in percent after 3 days (10)... w s 0.1 60

0.01 100 (CH O);PN-N

C H5-PO C Ha ll C HsO S (11)... 0. 1 100 H 0.01 100 2 50): PN--NC2H50'1.?-O CHa (12)... 02115 S O. 1 100 ll 0. 01 100 C2H5OPN--N(CHaOJzfi-O CH:

(13)... C lls S 0. 1 100 II 0.01 05 CzH50P-N--N (CgHsOhfi-O -CH3 (14)...CzHs S 0. 1 100 5) 0. 01 100 C 2H50- P-NN (C2 s)2 -CHa (15)... CrHs S 0.1 100 I! 0. 01 95 CQH50 P.\'N CzH-PO H-CH! ll CgH50 S EXAMPLE 3 Myzystest (contact action) Solvent Emulsifier: 3 parts by weight of acetone 1part by weight of alkylaryl polyglycol ether To produce a suitablepreparation of the particular active compound, 1 part by weight of theactive compound is mixed with the stated amount of solvent containingthe stated amount of emulsifier and the concentrate is diluted withwater to the desired final concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the preparation of theactive compound until dripping wet.

After the specified period of time, the degree of destruction isdetermined as a percentage: 100 percent means that all the aphids arekilled whereas 0 percent means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from Table 3.

Degree of destruction in percent in percent after 24 hours TABLE 3Continued Myzus test Active com- Degree of pound condestructioncentration in percent Active compound (constitution) in percent after 24hours wun N EXAMPLE 4 Tetranychus lest Solvent Emulsifier: 3 parts byweight of acetone 1 part by weight of alkylaryl polyglycol ether Toproduce a suitable preparation of the particular active compound, 1 partby weight of the active compound is mixed with the stated amount ofsolvent containing the stated amount of emulsifier and the concentrateso obtained is diluted with water to the desired final concentration.

Bean plants (Phaseolus vulgaris) which have a height of approximatelylO-30 cm., are sprayed with the preparation of the active compound untildripping wet. These bean plants are heavily infested with spider mites(Tetranychus urticae) in all stages of development.

After the specified period of time, the effectiveness of the preparationof the given active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:I00 percent means that all the spider mites are killed whereas 0 percentmeans that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from Table 4.

TABLE 4 Tetranychus urticae resistant/Wiesmoor Active com- Degree ofpound condestruction centration in percent Active compound(constitution) in percent after 48 hours N CH;

(known) (B) I? 0. l 0

(C2H50)2 P-O \N/ C H3 (known) ll (CH30)zP-N-N (CgH50)zfi-O ICH3 ll 25O)zP-N-N (CH 0)2PO CH:

ll ((321150); PN-N 7 S ll 0. 1 100 (0211 0); PNN

(Cg[I50)zfi-O C":

(8) o g 0. l 100 (C2H50)2PNN ll (C1H50)gP-NN C2H5\ C H:

PO CzHsO S (13) CzHs S 0. 1 90 PNN CzHsO CH s (011150): h e

(14). (7 S 0.] ill() l -NN 1 I50 (i l l 5 (0211 0); :1

'IABLE 4 Continued (e.g. mg/l isdecisive. The soil is filled into potsand the pots are left to stand at room temperature. After 24 hours thetest insects are put'into the treated soil and Actlvelcmnd Dtegrettl: ofafter a further 48 hours the degree of effectiveness of "3,135,511,", {123 the active compound is determined as a percentage by Aotlvn cmnpmuul(constltutlon) in percent alter 48 hours ti th d d d li i t i t Thdegreeyof effectiveness is 100 percent when all the test insects'I'rlram c/ius urlicac reslsLant/Wlcsmoor 2 II have been killed; it is 0percent when exactly as man l'-N-N y test insects are still alive as inthe case of the control. @2115" I on: The active compounds, the amountsapplied and, the K results can be seen from Table 5. CzIhO S EXAMPLE 67' v S EXAMPLE 5 cH 0 i -N-N Critical Concentration Test/Soil InsectsTest insect: Cabbage fly maggots (Phorbia (O2H5O)2fiO CH3 brassica) S(1) Solvent: 3 parts by weight of acetone 83 g of the sodium salt of0,0-diethyl-( 3-methyl-5- 1 1 1 11 Po yg yco e! Hhydroxy-pyrazolyl-l)-thionophosphoric acid ester in 400 ml of acetoneare reacted with 57 g of 0,0- diethylthionophosphoric acid esterchloride for 2 hours at 50 to 60 C. Thereafter the batch is poured intowater, extracted by shaking with benzene, the benzene extract is dried,the solvent evaporated and the residue slightly distilled.

The yield is 108 g (90 percent of the theory) and the refractive index:n 1.5052.

Calculated for C H ,O N,S P (molecular weight To produce a suitablepreparation of the particular active compound, 1 part by weight ofactive compound is mixed with the stated amount of solvent, the statedamount of emulsifier is added and the concentrate is diluted with waterto the desired final concentration. The preparation of active compoundis intimately mixed with the soil. The concentration of the activecompound in the preparation is of practically no importance; only theamount by weight of active compound per unit volume of soil, which isgiven in p.p.m., 402):

TABLE 5 6 51 s P 15.9%; 15.4% Phorbmtest Found: 7.12%; 15.96%; 15.60%.

Activg D f A com oun egreeo conem. destruction The following compoundscan be manufactured Active compound (constitution) tion in p.p.m. inpercent analogously: (1o) s 20 100 ll 10 9o (C3l[6U)gl-N-N 40 S s(C2H,O)zi NN -01i= 0111 1 4) (C2H50)zP-O CH3 ugmo (7) N Y1eld: 96percent of theory, refract1ve mdex: n,,

s 1.4850 H 0H1 Calculated for C H O N SP (molecular weight CzHh-P- 386):CzHBO ,N WP. i 8 r 7.25%; .s.3%; 16.10%; (CH30),P N N Found: 7.64%;8.20%; 16.31%.

(CzH50)3PO CH3 ll (OzH O)zPNN l6 c H s 20 96 z fl\" lo 5 (CH3)2N CH3/l-NN P-O 0,1110 l (CHmN 16 CH; -a f n 0,H1-P-0 021110 s Yield: 92percent of theory, refractive index: u (o)... s N=CCH: 2o 0 15069 0Calculated for C H O N SP (molecular welght (CgHn0)2PN c cH= 0 N s P14.6%; 8.35%; 16.15%; (known) Found: 14.77%; 8.25%; l6.23%.

Yield: 93 percent of theory, refractive index: n

Calculated for CnHgoOsNzSgPg (molecular weight Yield: 95 percent oftheory, refractive index: n 1.5580

Calculated for C H O N S P (molecular weight S P 14.75%; 14.3%; Found:14.47%; 14.51%.

H 2Hs0)2 N N CzH5-P-O CH3 czHso S Yield: 92 percent of theory,refractive index: n 1.5200

Calculated for C, H O N S P (molecular weight 386):

N S P 7.25%; 16.6%; 16.1%; Found: 7.52%; 16.41%; 16.37%.

The sodium salt of 0,0-diethyl-(3-methyl-5-hydroxypyrazolyl-l)-thionophosphoric acid ester required asthe starting material can for example be obtained as follows:

S P 10.8%; 10.5%; Found: 10.77%; 10.58%.

NaO H g. of the 0,0-diethylthionophosphorylhydrazono-acetoacetic acidethyl ester, dissolved in 400 ml of benzene, are mixed with 0.4 mol ofsodium ethylate at 20 to 35 C. After stirring the mixture for 2 hours,the precipitate which has formed is filtered 011 and dried.

The yield is 60 g (55 percent of theory) and the melting point of theproduct is 157 C.

Calculated for C l-l O N sPNa (molecular weight 272):

N S P Na 10.3%; 11.8%; 11.4%; 8.5%; Found: 9.74%; 11.79 11.22%; 8.79%.

EXAMPLE 7 (CHsOhlT-O CH;

A solution of 74 g of the sodium salt of 0,0-dimethyl-[3-methyl-S-hydroxypyrazolyl-l l-thionophosphoric acid ester in 400 m1of acetonitrile is mixed with 49 g of 0,0-dimethyl-thionophosphoric acidester chloride at 30 to 40 C. After stirring the mixture for 2 hours at30 to 40 C, benzene is added, the batch is extracted by shaking with alittle water, the benzene phase is separated off and dried, the solventis removed and the residue is slightly distilled. The yield is 96 g (92percent of theory) and the refractive index: n 1.5279.

Calculated for C H O N S P (molecular weight 346):

N S P 8.1%; 18.5%; 17.9%; Found: 8.47%; 18.33%; 18.11%.

The following products are obtained analogously:

Yield: 98 percent of theory, refractive index: u 1.5304.

Calculated for C l-l O N S P (molecular weight 358):

S P 17.9%; 17.3%; Found: 17.93%; 17.4%.

Yield: 91 percent of theory, refractive index: u 1.4929

Calculated for C H O N SP (molecular weight 358).

Found; 8.89%; 17.01%.

Yield: 86 percent of theory, refractive index: n 1.5165

Calculated for C H O N S P (molecular weight 374) N S P 7.5%; 17.1%;16.6%; Found: 7.98%; 16.09%;

The requisite starting material can for example be manufactured asfollows:

Nao CH3 Found: 9.41%.

EXAMPLE 8 52 g of the sodium salt of -ethyl-ethane-( 3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphonic acid ester in 300 ml ofacetonitrile are mixed with 35 g of 0- ethylethanethionophosphonic acidester chloride. After 3 hours stirring at 40 to 50 C the batch is pouredinto water and taken up in benzene, the benzene phase is separated offand dried, the solvent is stripped off and the residue is slightlydistilled.

The yield is 69 g (93 percent of theory), refractive index: n 1.5296.

Calculated for C H O N S P (molecular weight 370) S P 17.3%; 16.8%;Found: 17.4%; 17.1%.

The following can be manufactured analogously:

(1 2H5O-PN-N Yield: 93 percent of theory, refractive index: n 1.5171

Calculated for C, H O N S P (molecular weight 386) P 16.1%; Found16.09%.

CzHs S I C2H50-.l N--N (CgH50)2]|T-O l CH3 Yield: 95 percent of theory,refractive index: n

Calculated for C 1-1 O N SP (molecular weight 370) N S P 7.6%; 8.65%,16.8%; Found: 7.69%; 8.45%; 16.82%.

CgH OPN-N Yield: 91 percent of theory, refractive index: n 1.5286

Calculated for C 1-1 O N S P (molecular weight 358) N S P 7.85%; 17.9%;17.3%; Found: 8.02%; 17.7%; 17.51%.

CzHgO llqN 1 l (CH:)2N CH3 P-0 /|l (CH:)2N O (17) Yield: 90 percent oftheory, refractive index: u 1.5170.

Calculated for C H O N SP (molecular weight 368) S P 8.7%; 16.85%;Found: 8.88%; 17.3%.

The requisite starting material is for example obtainable as follows:

CzHsO (IVb) 168 g. of O-ethylethanethionophosphonic acid hydrazide in500 ml of benzene is mixed with g of acetoacetic acid ethyl ester andthe'water produced in the reaction is distilled off azeotropically.Thereafter the solvent is stripped off and the residue is slightlydistilled.

The yield is 276 g (99 percent of theory), refractive index: n 1.5011.

N s P 10.0%; 11.4%; 11.1%; Found: 10.41%; 10.86%; 10.92%.

CzHs S \PN--N 0,1150 1 J NuU- on 280 g of the(l-cthyl-ethancthionophosphonylhydrazonoacetoncctic acid ethyl estermanufactured as above, in 800 ml of benzene, are mixed with 1 mol ofsodium methylate at C. After stirring the mixture for 1 hour, theprecipitate which has formed is filtered off and dried on a clay plate.The yield is 219 g (86 percent of theory). The melting point is 200 C.

Calculated for C l-l O N SPNa (molecular weight 256) N s P Na 10.9%;12.5%; 12.1%; 9.0%; Found: 11.2%; 12.63%; 12.33%; 8.97%.

EXAMPLE 9 (C2HaO)2] N-N (CHIIO)ZII-TO K/ OHQ 53 g of the sodium salt of0,0-diethyl-( 3-methyl-5- hydroxy-pyrazolyl-l )-phosphoric acid ester in300 c.c. of acetonitrile are stirred with 33 g of 0,0-dimethylthionophosphoric acid ester chloride for 3 hours at to C.Thereafter the batch is poured into water and taken up with benzene, thebenzene phase is separated off and dried, the solvent is stripped of andthe residue is slightly distilled.

The yield is 58 g (81 percent of theory) refractive index: n 1.4865.

Calculated for C H O N SP (molecular weight 358) N S 7.8%; 8.95%; Found:7.79%; 9.82%.

The following compound is obtained analogously:

The sodium salt of the 0,0-diethyl-( 3-methyl-5-hydroxy-pyrazolyl-l)-phosphoric acid ester, which serves as the startingmaterial, can for example be obtained as follows:

Nao- CH:

(IId) 168 g of 0,0-diethylphosphoric acid hydrazide are gradually mixedwith 130 g of acetoacetic acid ethyl ester. After 30 minutes the mixtureis diluted with 500 ml of benzene and dried over sodium sulphate, thedry benzene solution together with 1 mol of sodium methylate is stirredfor 1 hour, and the solvent is subsequently stripped off.

The yield is: 217 g percent of theory).

Na Calculated for C H O,N PNa (molecular weight 256) 9.0%, Found: 8.5%.

It will be realized that all of the foregoing compounds contemplated bythe present invention possess the desired selective pesticidal,especially arthropodicidal, i.e., insecticidal or acaricidal, propertiesfor combating insects and acarids, and that such compounds have a lowphytotoxicity and a correspondingly low mammalian toxicity.

As may be used herein, the terms arthropod, arthropodicidal andarthropodicide contemplate specifically both insects and acarids. Thus,the insects and acarids may be considered herein collectively asarthropods to be combated in accordance with the invention, andaccordingly the insecticidal and/or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used will be an arthropodicidally effective amount which ineffect means an insecticidally or acaricidally effective amount of theactive compound for the desired purposes.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What we claim is:

1. A (thiono) phosphoric (phosphonic)-acid ester of the formula in whichR and R are straight-chain or branched lower alkyl X and X are oxygen orsulphur,

R is straight-chain or branched lower alkyl, lower alkoxy, mono-loweralkylamino or di-lower alkylarnino or phenyl, and

R is straight-chain or branched lower alkyl or lower alkoxy.

2. Compound according to claim 1 wherein R and R' are alkyl of one tofour carbon atoms, R" has one to four carbon atoms in each alkyl groupor is phenyl, and R has one to four carbon atoms.

3. Compound according to claim 1 wherein such compound is the0,0-di-methyl-thionophosphoric acid ester 0,0-ethyl-(3-methyl-5-hydroxy-pyrazolyl- 1 thionophosphoric acid ester of theformula 5. Compound according to claim 1 wherein such compound is the0,0-di-ethyl-thionophosphoric acid ester of0,0-diethyl-(3-methyl-S-hydroxy-pyrazolyLl thionophosphoric acid esterof the formula k ILOEB 6. Compound according to claim 1 wherein suchcompound is the 0,0-di-ethyl-phosphoric acid ester of 0,0-di-ethyl-(3-methyl-S-hydroxy-pyrazolyl-1 thionophosphoric acid ester of theformula 7. Compound according to claim 1 wherein such compound is the0,0-di-ethyl-phosphoric acid ester of 0,0-diethyl-(3-methyl-5-hydroxy-pyrazolyl-1 phosphoric acid ester of the formula (CgHOhP-O CH:

8. Compound according to claim 1 wherein such compound is theO-ethyl-ethane thionophosphonic acid ester of 0,0-dimethyl-(3-methyl-5-hydroxy-pyrazolyll )-thionophosphoric acid ester of theformula II HaO)2P NN CQis 5 PO CH5 9. Compound according to claim 1wherein such compound is the O-ethyl-ethanethionophosphonic acid esterof 0,0-diethyl( 3-methyl-S-hydroxy-pyrazolyLl thionophosphoric acidester of the formula (CzH5O)2] --NN C 2H5 CH3 P-O C2H50/ g 10. Compoundaccording to claim 1 wherein such compound is the0,0-di-methyl-thionophosphoric acid ester of0-ethyl-(3-methyl-S-hydroxy-pyrazolyl-1)- ethanethionophosphonic acidester of the formula (CHaOhlT-O -CHs 11. Compound according to claim 1wherein such compound is the 0,0-di-ethyl-phosphoric acid ester ofO-ethyl-( 3-methyl-5-hydroxy-pyrazolyll ethanethionophosphonic acidester of the formula C2H5 S o2mo NN 2H5 )2fi CH:

12. Compound according to claim 1 wherein such compound is the0-ethyl-ethanethionophosphonic acid ester of0-ethyl-(3-methyl-5-hydroxy-pyrazolyl-l)- ethanethionophosphonic acidester of the formula o2115 i -N-N C2H5PO CH3 C2H5O S Ulx'l'j'c'lfll).S'IA'll'iffi E.A I INT OFFICE CER'HIFIEGATE OF CORRECTION Patent No. 3700 Dated October 1972 Inventor s Hellmu t Hoffmann et a1 It iscertified that: error nppears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 3', line 23 delete "propyl-methane-phosphonyl) Column 4,1ine 42,change "apply" to --apple--.

Column 4, line 57, change "lepidoptera) to --(Lepidoptera) Column 7,line 59, Column 9 line 65,

Column 11, line 49, and 4 Column 13, line 45, cancel "Solvent,Emulsifier" and substitute therefor:

-*-Solvent:--

--Emulsifier Column 15, Table 5, Compound (10) cancel "(C H O) andsubstitute therefor --%C H O) Column 19, line 14, under "S" insert17.01% under "P" insert 16.39%

Column 22, line 61, claim 3 cancel "0 ,O-thyl" and substitute therefor--0,0-di-ethyl--.

Signed and sealed this 8th day of May 1973.

(SEAL) Attest:

EDWARD 1-I.FLETCHER,JR. ROBE LT GOTTSCHAIK Attes'ting OfficerCommissioner of Patents

2. Compound according to claim 1 wherein R and R'''''' are alkyl of oneto four carbon atoms, R'''' has one to four carbon atoms in each alkylgroup or is phenyl, and R'' has one to four carbon atoms.
 3. Compoundaccording to claim 1 wherein such compound is the 0,0-di-methyl-thionophosphoric acid ester0,0-ethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphoric acid esterof the formula
 4. Compound according to claim 1 wherein such compound isthe 0, 0-di-methyl-thionophosphoric acid ester of0,0-di-ethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-phosphoric acid ester ofthe formula
 5. Compound according to claim 1 wherein such compound isthe 0, 0-di-ethyl-thionophosphoric acid ester of0,0-diethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphoric acid esterof the formula
 6. Compound according to claim 1 wherein such compound isthe 0, 0-di-ethyl-phosphoric acid ester of0,0-di-ethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphoric acidester of the formula
 7. Compound according to claim 1 wherein suchcompound is the 0, 0-di-ethyl-phosphoric acid ester of0,0-diethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-phosphoric acid ester ofthe formula
 8. Compound according to claim 1 wherein such compound isthe 0-ethyl-ethane thionophosphonic acid ester of0,0-dimethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphoric acidester of the formula
 9. Compound according to claim 1 wherein suchcompound is the 0-ethyl-ethanethionophosphonic acid ester of0,0-diethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-thionophosphoric acid esterof the formula
 10. Compound according to claim 1 wherein such compoundis the 0,0-di-methyl-thionophosphoric acid ester of0-ethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-ethanethionophosphonic acidester of the formula
 11. Compound according to claim 1 wherein suchcompound is the 0,0-di-ethyl-phosphoric acid ester of0-ethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-ethanethionophosphonic acidester of the formula
 12. Compound according to claim 1 wherein suchcompound is the 0-ethyl-ethanethionophosphonic acid ester of0-ethyl-(3-methyl-5-hydroxy-pyrazolyl-1)-ethanethionophosphonic acidester of the formula